Dyeing fabrics containing cellulosic material and cellulosic material treated with quaternary nitrogen compounds



Patented Nov. 4, 1947 FFlCE DYEING FABRICS CONTAINING CELLULOSIC MATERIAL AND CELLULOSIC MATERIAL TREATED WITH QUATERNARY NITROGEN COMPOUNDS Glenn F. Womble, Danville, and Paul Feldmann, Schooifleld, Va., assignors to Dan River Mills, Incorporated, a corporation oi Virginia No Drawing. Application September 18, 1943,

Serial No. 502,972 a 9 Claims. 1

Our invention relates to dyeing of cellulose and more particularly to changing the dyeing properties of natural or regenerated cellulose materials such that they become relatively immune to dyestuffs commonly used therefor, but recepifaive to other dyestuffs not usually suitable there- The natural cellulose materials, e. g., cotton, flax, jute, hemp, sisal, and wood fibers, are normally dyed with direct, sulfur, naphthol, or vat dyestuifs, for which they have an amnity. The same is generally true for the regenerated cellulose materials, commonly referred to as -viscose rayons and made by the cuprammonium, nitrocellulose or viscose processes. For sake of convenience and brevity, these dyestuffs, which are commonly used for dyeing natural and regenerated cellulose, are referred to hereafter as "cotton dyes."

One particular class of rayons, which are not regenerated cellulose but are chemically acetic esters of cellulose, e. g., cellulose acetate, are referred to commercially as acetate'silks. They are commonly dyed with a different class of dyestufis than those mentioned above, namely, cellu lose acetate dyestuffs. The latter are referred to hereafter as acetate dyes.

These acetate dyes have an affinity for" the cellulose acetate rayons and are therefore normally used for dyeing such materials. But they will not satisfactorily dye viscose rayons or natural cellulose materials, which are usually dyed with the cotton dyes.

In accordance with our invention we have discovered that by chemically treating the cellulosic materials comprising natural or regenerated cellulose, with certain chemical compounds idenof natural or regenerated cellulose to which the chemical compounds identified hereafter may he applied.

The extent or degree 'of modification of th dyeing properties produced .by our invention varies with the concentration and reaction of the chemical employed. We have found it advantageous is intended to cover all suitable physical forms to repeat the application of the modifying chemicals on the cellulosic materials instead of using higher concentrations of the chemicals to acquire a desired effect; but either or both of these procedures may be used.

A variety of color effects can be obtained by treating the cellulosic materials in various steps of their manufacture, and also by following various dyeing procedures. For example, if indi-'- vidual fibers are treated with the chemicals of our invention prior to dyeing, heather effects are obtained upon dyeing; whereas if yarns are thus treated, stripes or checks result. Similarly, distinctive color effects are obtained by crossdyeing (i. e., dyeing treated and untreated fibers simultaneously in the same dye bath) which results in contrasting shades; or dyeing either treated or untreated portions of yarn or fabric to produce thereby white and colored effects. In some instances the chemical treatment does not render the cellulosic material entirely immune to dyeing with dyestuffs normally employed for such material, but, nevertheless, inhibits the usual intensity of dyeing, which results in different shades.

Regarding the chemical compounds that may be used to obtain some or all of the desirable effects characteristic of our invention, we have found that they can be identified by the ing general formula:

in which X stands for oxygen, or for CO--NR' and R represents hydrogen or an aliphatic hydrocarbon radical; R stands for an aliphatic hydrocarbon radical of at least five carbon atoms when X stands for CO--NR; and R stands for an aliphatic hydrocarbon radical of at least twelve carbon atoms when X stands for oxygen; said carbon atoms may be normal or branched, may or may not contain double bonds, or may be of a more complicated'structure; N (tert) stands for a tertiary amine that may be aliphatic or heterocyclic; and Y stands for halogen or for an anion of a water soluble acid.

We have obtained the'new results of our invention by applying one or more of these chemical compounds, which are unstable, quaternary ammonium bases, and heating the thus treated materials. The heating causes decomposition of the chemical; and apparently a, reaction takes place between the decomposition products and the cellulose of the material such that some transformation of the fiber results. The effect on the dyeing properties of the material is a marked followchange in amnity from Although we do not wishto be limited to an theory for explaining the surprising results of our treatment, we believe that the cellulose is attacked chemically and that a new and different cellulose compound is formed. This is sug-.

gested not only by the immunization of the cellulosic materials toward dyes for which" they normally have an afllnity but even more strongly indicated by the establishing of an entirely new property, namely, an ailinity of the cellulosic ma-- terials for the acetate dyes that normally willnot e to the other of the I two classes of dyes, above mentioned. 1

*In treating the cellulosic materials with one or mbre of the foregoing chemicals, suflicient heat '15 applied to cause decomposition of the chemical and coaction or reaction with the cellulose to eil'ect the change in, dyeing properties, above described. Both temperature and time of treatment may be widely varied, for example, temperatures of about 140 F. to 390- Rand times of about one minute to one or more hours may be dye these cellulosic materials. Irrespective or any theory, these changes illustrate the new and unexpected results of our invention.

The quaternary ammonium compounds cov-' ered by the above general formula may be subdivided into two principal classes according to the following two formulae:

(1) R-OCH:N(tert) Hal 7 in which R is an aliphatic hydrocarbon radical of at least twelve carbon atoms that may be nor me] or branched, may or may not contain double bonds or may be more complicated as in naphthenyl alcohol; 'N (tert) stands for a tertiary amine'which may be. aliphatic or heterocyclic; and Hal stands for a halogen ion.

The compounds identified by this formula are quaternary ammonium compounds formed from certain alcohols, formaldehyde, and salts of tertiary ammonium bases, and are characterized by containing at least twelve carbon atoms. They decrease the aflinity for the cotton dyes and increase the aflinity for the acetate dyes.

The formula representing the second class of compounds is as follows:

R 2 R-C0 I-0HsN(tert)X in which It represents an aliphatic hydrocarbon radical containing at least five carbon atoms. It may be normal or branched, may or may not contain double bonds or may be of a more complicated structure as for instance when the radical R--CO- is represented by the radical of a naphthenic acid; R stands for hydrogen or an aliphatic hydrocarbon'radical; N (tert) stands again for a tertiary amine which may be allemployed; the higher temperatures naturally requiring shorter time of treatment and vice versa. The time and temperature are also adjusted to avoid injury to the fiber.

Illustrative but non-limiting examples of practical applications of the method of our invention now follow:

. Example L-Me rcerizedbleached cotton poplin J is impregnated through an immersion padder at 120 F. with a 6% solution of octadecyl oxymethyl pyridinium chloride and 4% of sodium acetate, therebytaking up an amount of solution equal to the-weight of material padded; dried at a low temperature and subsequently cured in an a at 120 F. to remove the decomposition products.

even for 3 migutes at 290 F., and washed with soda ash and a detergent, namely, a substituted I amide of oleic acid, CnHaaCONMeC-HzCHzSOaNa A swatch of this treated material was immersed for 20 minutes along with a portion of untreated material of the same construction, in a dyebath containing 2% of a direct and developed black dye (color index No. Pr. 147) at 180 F. The

treated material was not dyed, while the untreatstained.

phatic or heterocyclic; and X stands for the I anion of a water soluble acid.

These compounds are quaternary ammonium compounds formed from fatty acid amides, formaldehyde and tertiary ammonium salts. It should be noted that they may contain as few as five carbon atoms in the aliphatic hydrocarbon radical R.

Specific but non-limiting examples of the compounds that may be used to produce the novel dyeing properties of cellulosic materials in accordance with our invention are:

Octadecyl oxymeth'yl pyridinium chloride Lauryl oxymethyl-pyridinium chloride Stearamido methyl pyridinium chloride Stearamidomethylpyridinium nitrate Stearamidpmethylpyridinium bromide Oleylamidomethylpyridinium chloride Lauramidomethylpyridinium chloride N-methyl-stearamido methyl trimethylammonium bromide Caproamido methyl pyridinium chloride Cetyl oxymethyl-ethyl-dimethyl-ammonium nitrate ed portion was dyed a satisfactory shade of black. Likewise. a swatch of treated material was immersed for 20 minutes along with an untreated portion of thesame material into a bath containing 2% of a direct, on acetate rayon, blue dye at 160 F. The treated portion was dyed blue and the untreated portion was only slightly Example 2.Skeins of mercerized bleached cotton yarn were impregnated with 5% solution of lauryl oxymethyl-pyridinium chloride, and 3.5% of sodium acetate at room temperature, squeezed, dried at room temperature in the air and subsequently cured for 30 minutes at 220 F, in an 'oven withcirculating air, washed with a detergent, namely, a substituted amide of oleic acid, C17H33CONME.CH2CH2SO3Na and soda ash at F. to remove the decomposition products.

I A portion .of above treated yarn along with a were dyed with a green vat dye (color index No.

1101), a red vat dye (color index No, Pr. 124), a brown vat dye (color index No. Pr. 118), and a yellow vat dye (color index No. Pr. 9), respectively. Then these vat dyed skeins along with an undyed skein were dried, impre nated with 6% stearamido methyl pyridinium chloride and 4% sodium acetate, dried at moderate temperature, cured in an oven at 300 F. for 3 minutes, washed with soda ash and a detergent, namely, a substituted amide of oleic acid,

- CnHaaCONMaCHaCHaSOaNa to remove the decomposition products and then dried. Threads from each of above treated skeins were sewn into a swatch of bleached mercerized cotton broadcloth to represent stripes or colored designs, then this swatch was dyed at 180 F. with 2% of a direct and developed black dye (color index No. Pr. 147) for minutes. After rinsing and drying we found the cotton cloth had dyed black and the treated yarn was not dyed by the black dye; thus giving a multi-colored effect.

Example 4.-Exact procedure as above was followed except the swatch was dyed with 2% of a black vat dye. The same multi-colored effect was obtained except the treated yarns were slightly stained, but still showing relative immunization.

Example 5.A swatch of mercerized bleached cotton broadcloth was padded with 3% stearamido-methyl-pyridinium chloride and 2% sodium acetate, dried at moderate temperature, cured for 3 minutes at 295 F., washed witha detergent, namely, a substituted amide of oleic acid,

and soda ash, dried and the same treatment re peated. That is, a double treatment was given. The double treated swatch along with an untreated swatch of the same material were cross dyed in a bath at 180 F. containing a direct and developed black dye (color index No. Pr. 147) and a direct, on acetate rayon, red dye. The result was, that the untreated swatch dyed a satisfactory shade of slate and the treated swatch dyed a satisfactory shade of rose,

Example 6.A swatch of the above treated material was padded along with a swatch of un treated material through a solution of 20 grams per liter of a sulfuric acid ester of a leuco vat dye (color index No. 1114) and 7.5 grams per liter of sodium nitrite and developed in an oxidizing bath of grams per liter of sulfuric acid. The untreated swatch was dyed a medium shade of blue while the treated swatch remained undyed.

Various modifications and changes may be made in the materials, compounds, and procedures described above without departing from the scope of our invention, some of the novel features of which are defined in the appended claims.

We claim:

l. A method of dyeing mixtures of treated and untreated cellulosic materials, comprising first impregnating some of said materials with a solution containing a compound of the formula where in R represents an aliphatic hydrocarbon radical containing at least five carbon atoms, R is a member of the group consisting of hydrogen and aliphatic hydrocarbon radicals, N (tert) stands for a tertiary amine selected from the group consisting of aliphatic and heterocyclic amines, and X stands for an anion of a water soluble acid; then heating the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizing the treated cellulosic material for cotton dyes and imparting to said material an aflinity not theretofore possessed for acetate dyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting said mixture of materials to the action of a dye 4 r 6 i which causes some of the materials to be dyed and causes relatively no dyeing of the other materials, whereby novel color effects are produced in the mixture of materials.

2. A method of dyeing mixtures of treated and untreated cellulosic materials, comprising first impregnating some of said materials with a solution containing a compound of the formula wherein R represents an aliphatic hydrocarbon radical containing at least five carbon atoms, R. represents hydrogen, N (tert) stands for a pyridinium compound, and X stands for an anion of a water soluble acid; then heatin the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizing the treated cellulosic material for cotton dyes and imparting to said material an aflinity not theretofore possessed for acetatedyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting said mixture of materials to the action of a dye which causes some of the materials to be dyed and causes relatively no dyeing of the other materials. whereby novel color effects are produced in the mixture of materials.

3. A method of dyeing mixtures of treated and untreated cellulosic materials, comprising first impregnating some of said materials with a solution containing stearamido methyl pyrid niuin chloride. then heating the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizing the treated cellulosic material f or cotton dyes and imparting to said material an affinity not theretofore possessed for acetate dyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting said mixture of materials to the action of a dye which causes some of the materials to be dyed and causes relatively no dyeing of the other matrrials, whereby novel color effects are produced in. the mixture of materials.

4. A method of dyeing mixtures of treated and untreated cellulosic materials, comprising first impregnating-some of said materials with a solution containing lauramido methyl pyridinium chloride, then heating the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizing the treated cellulosic material for cotton dyes and imparting to said material an affinity not theretofore possessed for acetate dyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting said mixture of materials to the action of a dye which causes some of the materials to be dyed and causes relatively no dyeing of the other materials, whereby novel color effects are produced in the mixture of materials.

5. A method of dyeing mixtures of treated and untreated cellulosic materials, comprising first impregnating some of said materials with a solut on containing oleylamido methyl pyridinium chloride, then heating the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizing the treated cellulosic material for cotton dyes and. imparting to said material an affinity not theretofore possessed for acetate dyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting said mixture of materials to the action of a dye which causes someot the materials to be dyed and causes relatively no dyeing oi." the other materials, whereimpregnating some of said materials witlr a solu- I tion containing a compound of the formula n-c o-rt-cm-mam-x wherein R. represents an aliphatic hydrocarbon radical containing at least five carbon atoms, R is a member of the group consisting 01 hydrogen and aliphatic hydrocarbon radicals, N (tert) stands for a tertiary amine selected from the group consisting of aliphatic and heterocyclic amines, and X stands for an anion of a water soluble acid; then heating the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizi'ng the treated cellulosic material for cotton dyes and imparting to said material an affinity not theretoi'ore possessed for acetate dyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting saidmixture of materialsto the action of a direct dye which causes some of the materials to be dyed and causes relatively no dyeing of the other materials, whereby novel color effects are produced in the mixture 01' materials.

7. A method of dyeing mixtures of treated and untreated cellulosic materials, comprising first impregnating some of said materials with a solution containing a compound of the formula R-OO-N-CHz-NiterQ-X wherein R represents an aliphatic hydrocarbon radical containing at least five carbon atoms,R' is a member oi the group consisting of hydrogen and aliphatic hydrocarbon radicals, N (tert) stands for a tertiary amine selected from the group consisting of aliphatic and heterocyclic amines, and X stands for an anion of a water stands is a member or the group consisting oi hydrogen and aliphatic hydrocarbon radicals. N (tert) for a tertiaryamine selected from the group consisting of aliphatic and heterocyclic amines, and X stands for an anion or a water soluble acid; then heating the thus treated cotton fibers and causing a reaction between them and said compound, thereby substantially immunizing A the treated cotton fibers for cotton yes and imparting to said cotton fibers an aiilnity not there- ,tofore possessed tor acetate dyes, then mixing said treatedcotton fibers and untreated cotton fibers and subjecting said mixture of cotton fibers to the action ofa dye which causes some of the cottonfibers to be dyed and causes relatively no dyeing oi!v the other cotton fibers, whereby novel color eflects are produced in the mixture of cotton fibers.

9. A method of dyeing mixtures of treated and untreated viscose fibers, comprising first impregnating some of said viscose fibers with a solution containing a compound of the formula R-CO-lll-CHr-NfierO-X wherein R, represents an aliphatic hydrocarbon radical containing at least five carbon atoms, R is a member 0! the group consisting of hydrogen and aliphatic hydrocarbon radicals, N (tert) stands for a tertiary amine selected from the group consisting of aliphatic and heterocyclic amines, and X stands for an anion of a water soluble acid; then heating the thus treated viscose fibers and causing a reaction between them soluble acid; then heating the thus treated cellulosic material and causing a reaction between it and said compound, thereby substantially immunizing the treated cellulosic material for cotton dyes and imparting to said material an afllnity not theretofore possessed for acetate dyes, then mixing said treated cellulosic material and untreated cellulosic material and subjecting said mixture of materials to the action of a cotton dye which causes some of the materials to be dyed and causes relatively no dyeing of the other materials, whereby novel color effects are produced in the mixture of materials.

8., A method of dyeing mixtures 01' treated and and said compound, thereby substantially immunizing the treated viscose fibers for cotton dyes and imparting to said viscose fibers an ailin- -ity not theretofore possessed for acetate dyes, then mixing said treated viscose fibers and untreated viscose fibers and subjecting said mixture 01 viscose fibers to the action of a dye which causes some of the viscose fibers to be dyed and causes =relatively no dyeing of the other viscose fibers,

whereby novel color effects are produced in the mixture of viscose fibers.

GLENN F. WOMBLE. PAUL FELDMANN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

